Selected 13,14-diazatricyclo-(6.4.1.1**2,7) tetradecanes and diazatricyclo(6.4.1.1**2,7) tetradecatetraenes and their preparation



United States Patent 3,475,433 SELECTED 13,14-DIAZATRICYCL0-[6.4.1.1 TETRADECANES AND DIAZATRICYCLO [6.4.1.1 TETRADECATETRAENES AND THEIR PREPARATION Alexander L. Johnson, Wilmington, Del., assignor to E. L du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Feb. 25, 1966, Ser. No. 529,961 Int. Cl. C07d 51/72; G02b 5/22 US. Cl. 260268 16 Claims ABSTRACT OF THE DISCLOSURE Described and claimed are selected 13,14-diazatricycl0- [6.4.1.1 tetradecanes and diazatricyclo[6.4.l.1 ]tetradecatetraenes and their preparation. Tetraenes may be prepared by the thermal rearrangement of lH-azepine-lcarbonitrile dimers and may be hydrogenated to give the tetradecanes. The tetraenes and tetradecanes are all useful as adhesives. The tetraenes additionally are useful as ultraviolet light absorbers.

This invention relates to, and has as its principal objects provision of, compounds having a novel tricyclic heterocyclic ring system, i.e., certain 13,14-diazatricyclo- [6.4.l.1 ]tetradecanes and tetraenes, and processes for the preparation of the same.

In the Marsh US. Patent 3,268,512 of Aug. 23, 1966, the entire specification of which is incorporated herein by reference, there are described and claimed dimeric azepines of the general formula For the purposes of this invention, X represents certain substituents as defined more precisely below and m is a cardinal number in the range 06, inclusive, denoting the number of valences on the depicted carbons filled by substituents X. When m is less than 6, the valences on carbon up to a total of 6 not satisfied by substituents are satisfied by hydrogen. When m is greater than 1, the Xs need not be the same. A substituent can, of course, be located on any carbon in thering.

The exact structure of the dimers of the Marsh patent is not precisely known, but, in the case where no substituent is present (m=0), it is believed to involve the asymmetrical heterocyclic skeleton:

lH-azepine-l-carbonitrile dimers (Ia) 5,9-diazatetracyclo[552 00 ]tetradeca- 3,10,13-triene-5,9-dicarbonitrile The principal evidence for the la structure is found in the ultraviolet, infrared, and NMR absorption spectra and in ready reaction with Benedicts and Tollens re 3,475,433 Patented Oct. 28, 1969 "ice agents, indicating presence of C=C in an unsymmetrical environment and of groups. The dimeric N-cyanoazepines are readily soluble, physically stable, generally colorless compounds solid at normal temperatures and melting near 200 C.

As typical of the dimers of the Marsh patent, there may be considered the unsubstituted N-cyanoazepine dimer (Formula I, m=0; see Example 2 of the aforementioned Marsh patent), which is soluble in common solvents, melts at 215 C. with decomposition, and has the following spectral characteristics:

IR: vii; 1670 cmf (very intense), attributable to C=C in an unsymmetrical environment. UV: igg 241 In @5800), attributable to two I O H=C HNchromophores. NMR: (CD SO solution.

7:398 (m.), 6 protons; 5.07 (m.), 2 protons; 5.55 (m.), 2 protons; 6.24 (m.), 2 protons.

Attempts to hydrolyze or reduce this dimer lead to intractable mixtures, no products being formed that correspond to those obtained from the corresponding diazatricyclotetraene.

In accordance with the present invention, it has been found that, when heated near their melting points in a homogeneously diluted state, which may be a liquid or solid solution or a liquid, solid or liquid-solid mixture or dispersion, the N-cyanoazepine dimers of Formula I rearrange to more stable and novel diacyclotetracnes. An equation for the reaction taking place can be written as:

o=o o o ll it A C C diluent;

12 3 1 2 p (I! o4 Xmi 13 III-0N NCN 14 X... 10 o 5 8 7\ 9 0 (Ha) 13,14-diazatricyclo[6.4.1.1 ]tetradeca- 3,5,9,1 l-tetraene-l3,14-dicarb0nitriles In this equation, In represents a number from 0-6 being a maximum of 2 when X is nitro, while the Xs, alike or different, are selected from the group consisting of fluorine, chlorine, cyano, nitro, fluoroand chloroalkyl of up to 8 carbons and alkoxycarbonyl of up to 9 carbons. Preferably, m is 0 except when X is fluorine and then, preferably, it is 1, 2, or 6. It will be understood that all valences not obviously satisfied by C, N, or X are satisfied by H.

It may be noted that Formula II can be written to show the trans (IIb) and cis (IIc) stereoisomeric forms,

For the sake of simplicity, formulae of the type of He: rather than of IIb or II will be generally adhered to throughout this specification.

The dicarbonitriles of Formula 110 are readily prepared by mixing the corresponding precursor of Formula I with the chosen inert diluent, generally in the weight ratio of about 1:4 to 1:50, heating to the requisite temperature, generally in the range 175 to 300 C.., for -100 minutes or so, and recovering the desired product from the diluent by methods well understood in the art, e.g., by dissolution of either product or diluent in ap propriate solvents such as acetonitrile (for product), benezene (for naphthalene as diluent) or water (for salt as diluent). Any inert liquid or solid substance stable in the rearrangement temperature range can serve as a diluent. Examples of such diluents are naphthalene, silica sand, sodium chloride, palladium-on-charcoal, and selenium. If no diluent is used, however, heating the N-cyanoazepine dimer near its melting point causes vigorous decomposition to a degraded charred mass from which a recognizable product cannot be obtained. The degraded mass may contain some of the rearranged material, but separation of the latter would be impractical.

Compounds of Formula IIa are easily transformed to various derivatives which also form part of the invention. Thus, the cyano groups in the 13- and 14-positions can be hydrolyzed by well-known methods to yield the hydrolysis products. In addition, the double bonds can be hydrogenated to give the corresponding saturated compound either before or after the hydrolysis, All of the products can, of course, undergo typical class reactions to yield additional compounds. The formulae of the novel compounds of the invention can thus be written as H and III below, II including IIa (above) where R=CN:

IIc

Xm liI-R R-N Xm 13,14-diazatricyclo-[6.4.1.1] tetradeca-3,5,9,11-tetraenes and III

13,14-diazatricyclo-[6.4.1.1 tctradecanes In these formulae X and m are as above; R is cyano, hydrogen, nitroso [NO], alkyl [R of 1-8 carbons], carbarnoyl I II II [-(ilNHzl, alkylcarbamoyl [CNR'], arylcalbamoyl [-CNHAr -Ar being aryl hydrocarbon of 6-10 carbons], alkylthiocarbamoyl S O I ll [-PLNHR], arylthiocarbamoyl [-NHAr], alkylcarbonyl [-C R] O O I l arylcarbonyl J Ar], alkoxycarbonyl [-C O R], aryloxycarbonyl or aralkyl [R'Ar]; and Y is fluorine, chlorine, fluoroor chloroalkyl of up to 8 carbons, or alkoxycarbonyl. It will be noted that Y is of somewhat lesser scope than X because of the failure of certain radicals to survive the catalytic hydrogenation requisite to the method of preparation.

The hydrolysis of compounds of Formula Ila can be readily carried out in 50% sulfuric acid, for example. The products are the corresponding bis (ureas) 11d and diamines IIe (see below). Compounds 1111 result from short periods of treatment, specifically up to six hours, while compounds IIe are produced by more extensive heating, specifically up to 20 hours. Compounds IId may be converted to the usual secondary amine derivatives or isolated and purified in the form of amine salts, e.g., the hydrochlorides. Schematic equations for the hydrolysis reactions taking place may be written as follows:

| Xm NC-N N-CN Xm X...{ HN @Xm The diamines (Formula He) can be readily converted to compounds of Formula II wherein R is nitroso, alkyl, aralkyl, alkylor arylcarbonyl, alkoxyor aryloxycarbony], alkylor arylcarbamoyl, or alkylor arylthiocarbamoyl. The nitroso derivatives are obtained readily by usual amine nitrosation procedures, e.g., with sodium nitrite and hydrochloric acid (cf. Example 22). The derivatives where R is alkyl or aralkyl can be obtained by well-known alkylation procedures involving reaction of the diamines with corresponding halides, e.g., benzyl iodide (cf. Example 17). Reaction of the diamines with alkylor arylcarboxylic acid halides or anhydrides by conventional acylation procedures (cf. Examples 7 and 8) yields the derivatives in which R is alkylor arylcarbonyl; and acylation with alkyl or aryl haloformates yields the derivatives in which R is alkoxyor aryloxycarbonyl (of. Example 24). Similarly, by well-known methods, reactions of the diamines with alkyl or aryl isocyanates or isothiocyanates yield the compounds of Formula II in which R is correspondingly alkylor arylcarbamoyl or alkylor arylthiocarbamoyl, respectively (cf. Examples 9 and 14). Of course, the diamines of Formula He also form the usual hydrohalide salts such as the hydrochlorides or hydrobromides, which can be isolated from aqueous solution (cf. ExampleslO- and 12).

The new 13,14 diazatricyclo[6.4.1.1 ]tetradeca- 3,5,9,11-tetraenes of this invention are chemically stable, colorless solids which melt in the range -400 C. with decomposition. Their highly symmetrical cisoid diene structure is indicated by the nature of their infrared, ultra-violet, and NMR spectra (cf. Example 2), and of their Raman spectra (cf. Examples 5 and 17). Although they melt with decomposition, the products of meltdecomposition are not degraded and hence are useful adhesives. The compounds do not reduce Tollens and Benedicts reagents," and they are almost completely insoluble in most common solvents.

100 C 6 hrs.

Xm Xm Hydrogenation or some (lie) of the compounds II in aqueous hydrochloric acid over platinum catalyst at pressures of 1-5 atm. produce the corresponding octahydro-compounds ]I[b in the form of their hydrochlorides.

Compounds 'IIIb are colorless, pleasant-smelling materials which melt between -300 C. and show the usual secondary diamine properties.

The saturated diamines (Formula 1111)) can be readily converted to compounds of Formula IH wherein R is cyano, carbamoyl, nitroso, alkyl, aralkyl, alkylor arylcarbonyl, alkoxyor aryloxycarbonyl, alkylor arylcarbamoyl, or alkylor arylthiocarbamoyl. The derivatives where R is cyano can be obtained from the diamines by reaction with a cyanogen halide (Migrdichian The Chemistry of Organic Cyanogen Compounds, ACS- Monograph No. 105, p. 103) or by N-halogenation with alkali hypohalite followed by reaction with alkali cyanide (Taylor and baker, Sidgwicks Organic Chemistry of Nitrogen, Oxford University Press, 1945, pp. 40 and 329; Migrdichian, loc. cit., p. 132). The saturated cyano derivatives in turn can be hydrolyzed to the carbamoyl derivatives in the same fashion as the unsaturated cyano compounds of Formula IIa (cf. Examples 3 and 4). The nitroso derivatives are obtained conventionally by nitrosation (cf. Example 23). The derivatives where R is alkyl or arylalkyl can be obtained from the diamines and corresponding halides, e.g., amyl iodide, by wellknown alkylation procedures (cf. Example 18). The diamines and alkylor arylcarboxylic acid halides or anhydrides under conventional acylation conditions (cf. Example 13) yield the derivatives in which R is alkylor arylcarbonyl; and in the same fashion acylation with alkyl or aryl chloroformates yields compounds of Formula III in which R is alkoxyor aryloxycar-bonyl (cf. Example 24). Similarly, by well-known methods, reactions of the diamines with alkyl or aryl isocyanates or isothiocyanates yield the compounds of Formula HI in which R is correspondingly alkyl or arylcarbamoyl, or alkylor arylthiocarbamoyl, respectively (cf. Examples 15 and 16). The saturated diamines also form the usual hydrohalide salts (cf. Examples 10 and 12).

There follow some nonlimiting examples illustrating the invention in more detail. Example 1 represents a preferred method for preparing the dicyano compounds employed as precursors for the other compounds of the invention.

EXAMPLE 1.13,14 DIAZATRICYCLO[6.4.1.1 TETRDECA 3,5,9,11 TETRAENE 13,14 DI- CARBONITRILE Formula Ha: m=0 (or Formula II where R=CN and m=0) A -liter, 4-neck Morton flask equipped with heating mantle, mechanical stirrer, thermometer and two reflux condensers was charged with practical grade naphthalene (1000 g.). The thermometer bulb was arranged to dip into the naphthalene, and the condensers were heated with hot water. The apparatus was flushed with nitrogen and the temperature of the naphthalene was raised to 140 C., the stirrer being started when most of the naphthalene had melted (90 C.). Powdered dimer I (m=0; 200 g.) was added in minutes through one condenser to the rapidly stirred naphthalene at 140 C. The dimer dissolved rapidly and heating was continued until the temperature reached 190 C., when a slightly exothermic reaction began and compound Ila (m=0) started to precipitate. The temperature was maintained at 210 C. for 20 minutes, and then the mixture was allowed to cool with stirring to a temperature of C., when it was diluted with 2500 ml. of benzene. When the mixture had cooled to 60 C., it was filtered and the residue was washed thoroughly with 1250 ml. of benzene and airdried. The yield of pale brown crystalline 13,14-diazatricyclo[6.4.1.1 ]tetradeca 3,5,9,11 tetraene 13,14- dicarbonitrile was 138 g. (69%) of analytically pure material. The color was removed by continuous chromatography over F1orasil with dichloromethane as the eluant.

EXAMPLE 2.13,l4 DIAZATRICYCLO[6.4.l.l

TETRADECA 3,5,9,l1 TETRAENE 13,14 DI- CARBONITRILE (A) lH-azepine-l-carbonitrile dimer (Formula I, m=O; 40.0 g.) was mixed with IOU-mesh silica sand (1200 g.) and fed into the hopper of an inclined stainless steel auger reactor which had been preheated electrically for three hours at a jacket temperature of 250 C. The mixture was passed through the reactor at such a rate that a given sample had a contact time of 10 minutes. The brown product was extracted in a Soxhlet apparatus with acetonitrile to yield 23.95 g. (60%) of crude 13,14-diazatricyclo[6.4.1.1 ]tetraene-13,14-dicarbonitrile as a brown powder.

One half-gram of the crude product was purified by three recrystallizations from dichlorotetrafluoroacetone hydrate (3 ml.). The fine white powder was dried at 100 C./0.2 mm. (0.10 g.), M.P. 395 C. dec. Eleven grams of the crude product was purified more satisfactorily by continuous chromatography over a 1" layer of Florisil using dichloromethane as the eluant. Pure 13,14-diazatricyclo[6.4.1.1 ]tetradeca 3,5,9,11 tetraene-13,14-dicarbonitrile was recovered in 60% yield (6.62 g.)

(B) In a further experiment, a mixture of 37.0 g. of 1H-azepine-l-carbonitrile dimer and 1100 g. of sodium chloride was heated in the same apparatus, The sodium chloride was washed out with water and the residue, purified by continuous chromatography over Florisil, yielded 15.84 g. (43%) of pure 13,14-diazatricycl0[6.4.1.1 tetradeca-3 ,5,9,1l-tetraene-13 ,14-dicarbonitrile.

AnaIysis.Calcd. for C H N C, 71.16; H, 5.12; N, 23.72; M.W., 236.27. Found: C, 71.03, 71.36; H, 5.14, 5.13; N, 23.77, 23.74; M.W., 236 (mass spectrum).

IR: vfif; 3040cmf (w.) (CH=CH); 2210 GEL-1 (s.)

(GEN) 1660, 1625 cm- (w.) (0:0)

UV: xggg 237 m1. (e 16,300); 230 my (6 15,150)

(shoulder) MS: m./e. 230 (parent), 208, 195, 194., 193, 181, 169, 168, 167, 144, 119, 118 (base peak, parent),

NMR (CF CICOOF CI-DQO):

r=3.61 (m.) 8 CH=OH protons; 5.96 (d.) 4 CHN protons EXAMPLE 3.--13,14 BIS(CARBAMOYL) 13,14-

DIAZATRICYCLO [6.4.1 1 TETRADECA-3 ,5 ,9,1 l- TETRANE Formula 11: H

R=-C NHz; m=0

81%) filtered and washed with water. Two recrystallizations of 4.48 g. of this product from aqueous dichlorotetrafluoroacetone hydrate (20 ml.) with Darco-G60 treatment yielded 2.40 g. (53% recovery) of pure bis- (urea), 13,14 bis(carbamoyl) 13,14 diazatricyclo [6.4.1.1 ]tetradeca-3,5,9,1l-tetraene, M.P. 295 C. dec.

Analysis.CalCd. fOI C14H16N402: C, H, N, 20.58; M.W., 272.30. Found: C, 62.08, 62.02; H, 6.17, 5.98; N, 20.01; M.W., 272 (mass spectrum).

IR: 1155; 3420, 3300, 3160 cm.- (NHZ); 3000 emf (CH=CH); 1650, 1585 cm. (NCONH UV: egg 33 234. 31,. (e 9450 H protons; 5.32 (broad) 4 NFL exchange; protons +4 CHN; protons+solvent MS m./e.: 272 (parent), 229, 185, 169, 168, 136 (base peak, ,4 parent), 123, 118, 97, 93, 87, 85, 83, 81, 78, 71, 69, 57, 56, 55, 43, 31, 29, 28, 27, 18.

EXAMPLE 4.l3,l4 BIS(CARBAMOYL) 13,14- DIAZATRICYCLO[6.4.1.1 ]TETRADECA-3,5,9,1l- TETRAENE A mixture of 13,14-diazatricyclo[6.4.1.1 ]tetradeca- 3,5,9,1l-tetraene-13,14-dicarbonitrile (3.09 g.), paratoluenesulfonic acid 'monohydrate (9.97 g.) and water (5 ml.) was stirred together and heated at 110 C. for minutes. After cooling, the mixture was treated with water, basified with 25% sodium hydroxide and filtered. The insoluble residue (3.35 g., 90%) was identified as the bis(urea) of Example 3 by infrared spectrum.

EXAMPLE 5.13,l4 DIAZATRICYCLO[6.4.1.1 TETRADECA 3,5,9,ll TETRAENE FORMULA II: R=H; m=0

(A) Pure 13,14 diazatricyclo[6;4.1.1 ]tetradeca- 3,5,9,11-tetraene-13,14-dicarbonitrile (3.90 g.) and 50% sulfuric acid 50 ml.) were sealed in a polymer tube and heated at 100 for hours. After cooling to 0 C., the contents of the tube were diluted with 50 ml. of water and filtered free of 0.32 g. of the bis(urca), 13,14-bis- (carbamoyl) 13,14 diazatricyclo[6.4.1.1 ]tetradeca- 3,5,9,11-tetraene. The aqueous mother liquors were neutralized with solid sodium carbonate and adjusted to pH 8 with sodium bicarbonate before continuous extraction with chloroform. The crude diamine obtained by evaporation of the dried extracts weighed 1.86 g. (60% Recrystallization of 1.30 g. of this product from water with Darco G-60 treatment gave 0.51 g. of almost pure diamine 13,14 diazatricyclo[6.4.1.1 tetradeca-3,5,9,11- tetraene as white crystals, M.P. 142-144 C, A further recrystallization raised the melting point to 145-146.5 C. dec. after drying at C./0.2 mm.

Analysis.Calcd. for C H -N C, 77.38; H, 7.58; N, 15.04; M.W., 186.25. Found: C, 77.33; H, 7.72; N, 15.10, 14.84; M.W., 186 (mass spectrum.

IR: 1 235 3420, 3290 cm. (NH); 3030 crnf (CH=CH);

UV: ACHaCN 240 mu (6 15,800) (shoulder); 234 m,u (e

8 (B) In a further experiment, 68 g. of 13,14-diazatricyclo[6.4.1.1 ]tetradeca 3,5,9,11-tetraene-13,14-dicarbonitrile was hydrolyzed in a three-necked flask under nitrogen with 500 ml. of 50% sulfuric acid at 120 C. for 24 hours to give a yield of approximately 45% of 13,14- diazatricyclo[6.4.1.1 ]tetradeca-3,5,9,1l-tetraene.

EXAMPLE 6.-1 3 ,l4-DIAZATRICYCLO [6.4.1.1 TETRADECA-3,5,9,1 l-TETRAENE Example 5 was substantially repeated with the substitution of para-toluenesulfonic acid for sulfuric acid.

A mixture of 13,14-diazatricyclo[6.4.1.I Jtetradeca- 3,5,9,11 tetraene 13,14-dicarbonitrile (3.34 g.), paratoluenesulfonic acid monohydrate (10.78 g.) and water (0.5 ml.) was heated under reflux for two hours. The mixture was then stirred with 20 ml. of water and made alkaline with 25% sodium hydroxide solution. The alkaline mixture was continuously extracted with chloroform for 24 hours to yield 1.20 g. (46%) of the crude diamine of Example 5. Identification was confirmed by mixed melting point and n.m.r. spectrum, using a recrystallized sample, M.P. 144-146 C. dec.

EXAMPLE 7.-13,l4 DIBENZOYL-13,14-DIAZATRI- CYCLO[6.4.1.1 TETRADECA3,5,9,1 l- TETRAENE Formula II: H

R=-CC H 711 0 A suspension of 0.25 g. of 13,14 diazatricycio [6.4.l.1 ]tetradeca 3,5,9,11 tetraene (see Examples 5 and 6) in 5 ml. of 10% sodium hydroxide was shaken with 0.4 ml. of benzoyl chloride for 10 minutes. The precipitate was filtered, washed with water and air-dried (0.42 g., 79%). The crude product was recrystallized from 1:1 chloroform-ethanol (0.179 g.). After several recrystallizations, the benzoyl derivative was obtained as a white crystalline solid, M.P. 310311 C. dec. after drying at C./0.2 mm.

Analysis.-Ca1cd. for C H N O C, 79.16; H, 5.62;

N, 7.10. Found: C, 78.33, 79.87; H, 5.96, 5.44; N, 7.35, 7.21.

IR: v,,,,,, 3030 01117 (CH=CH); 1645 cmf (NOOO6H5); 1495, 1450, 14.20, 1360 cm? 0113) UV: xggg 235 m,u (6 21,300

EXAMPLE 8.13,l4 DI PARA-BROMOBENZOYL- 13,14 DIAZATRICYCLO[6.4.1 .1 TETRADECA- 3,5,9,l1-TETRAENE uv. tgg s NMR (CF- ClCOCF Cl-D O): r=3.20 (q., J=8c/s) 8 aromatic protons; 5.70 (m.) 8 vinyl protons; 6.85 (m.) 4 CH-N protons MS: m./e. 554, 552, 550 (parents), 278, 277, 276, 275 275 (1/2 parents), 264, 262, 186, 185, 184, 183 (base peak BI'CfiH4CO), 157, 155, 104, 92, 76, 75, 65, 39

EXAMPLE 9. 13,14 BIS(PHENYLTHIOCARBA- MOYL)-13,14-DIAZATRICYCLO[6.4.1.1 TETRA- DECA-3,5,9,1 l-TETRAENE Formula II: S H

R=-( I C6H5; 711

A 50% solution of phenylisothiocyanate (0.8 ml.) was added to a warm solution of 13,14 diazatricyclo [6.4.1.1 ]tetradeca-3,5,9,1l-tetraene (0.26 g.) in ethanol (1 ml.). After brief warming, crystals appeared and the mixture rapidly set to a crystalline mass. The residue was filtered and thoroughly leached with hot ethanol in a Soxhlet apparatus. The insoluble residue was dried at 100 C./0.2 mm., M.P. 21l212 C. dec.

Analysis.-Calcd. for C H N S C, 68.39; H, 5.30;

N, 12.27; S, 14.05; M.W., 456.616. Found: C, 68.23; H,

5.36; N, 12.05; S, 14.14; M.W.., 456 (mass spectrum).

IR: 115?; 3040 emf (W.) (CH=CH); 1600, 1520, 1510, 1450 cm? (m-s.) (C 11 1345, 1230 emf (s.) (NCSN) EXAMPLE 10.1 3 ,14-D-IAZATRICYCLO[6.4.1.1 TETRADECANE DIHYDROCHLORIDE Formula III: R:H; 4n:0 (plus 2 HCl) The unsaturated diamine 13,14-diazatricyclo[6.4.1.1 tetradeca-3,5,9,1l-tetraene (300 mg.) was dissolved in a mixture of water ml.), methanol (10 ml.) and cone. hydrochloric acid (0.5 ml.) and hydrogenated at C./760 mm. in the presence of 0.5 g. of platinum oixde. The mixture consumed 4 molar equivalents of hydrogen over a period of 5.5 hours. The catalyst was filtered, washed with water, and the filtrate and washings were evaporated to leave 239 mg. (56%) of a white crystalline solid. Two rccrystallizations from a mixture of water (3 ml.), acetone (6-10 ml.), and cone. hydrochloric acid (2 drops) gave pure material (65% recovery) as colorless crystals of the saturated diamine hydrochloride, 13,14 diazatricyclo[6.4.1.1 ]tetradecane dihydrochloride, M.P. 320 C. dec. after drying at 25 C./0.2 mm.

Analysis.Calcd. for C H N Cl C, 53.94; H, 9.06; N, 10.49. Found: C, 53.88, 53.51; H, 8.99, 8.94; N, 9.95, 9.96.

IR: 95;; 2980, 2860 cuton 2750 cut- NH,+

1575 emf (NI-12+) UV: no x532 210 mu NMR (D 0, 60 mc./s.): 'r=5.30 4 exchange protons; 6.00 4 CHN tertiary protons; 8.10 16 CH protons (D 0, 200 mc./s.): 7=5.30 4 exchange protons; 6.11 (d.) 4 CH-N protons; 7.89 (m.) Half of CH protons nearest bridgehead; 8.18 (m.) Other half of CH, protons nearest bridgehead+8 CH protons 10 EXAMPLE 11.13,14-DIAZATRICYCLO[6.4.1.1 TETRADECANE Formula III: R=H, m=0

Crude 13,14-diazatricyclo[6.4.1.1 ]tetradecane dihydrochloride (3.60 g.; see Example 10) was dissolved in 50 ml. of water, treated with 4 ml. of 30% sodium hydroxide, cooled to 0 C., and filtered. A small additional amount of material was obtained by continuous extraction of the mother liquors with carbon tetrachloride. The white crystalline product was purified by sublimation at 70 C./0.1 mm. to give pure 13,14 diazatricyclo [6.4.1.1 ]tetradecane: 2.13 g. yield); M.P. 61- 62 C. (sealed capillary).

Analysis.Calcd. for C H N C, 74.17; H, 11.41; N, 14.42; M.W., 194.31. Found: C, 74.06, 74.08; H, 11.13; 11.33; N, 14.36, 14.43; M.W., 194 (mass spectrum).

IR: 153; 3290 cm." (w.) (NH); 2900 cmf (w.) on

1450 cm.- (s.)(NH) 7315;? 3280 Omf (w.) (NH) UV: no A522 210 m NMR (C01 2): 7 729 (m.) 4 CHN protons; 8.29 (m.) 16 CH protons; 8.50 (s.) 2 NH protons; signals disappeared on shaking with D 0.

MS: m./e.194 (parent), 138, 124,122, 110, 108, 99, 98, 1 2 parent-I-H), 97, 95, 82, 59, 56, 4.2, 41, 28, 15

EXAMPLE 12.-1 3, 14-DIAZATRICYCLO [6.4.1 .1 TETRADECANE DIHYDROBROMIDE Formula III: RIH, m=0 (plus 2HBr) The mother liquors from the recrystallization of the saturated diamine 13,14-diazatricyclo[6.4.1.1 ]tetra- -decane (see Example 11) were acidified with 48% hydrobromic acid, treated with excess acetone and cooled to 0 C. The white precipitate was reprecipitated twice more with aqueous acetone to give the dihydrobromide (63 mg.), M.P. 320 C. dec.

Analysis.Calcd. for C H N Br C, 40.47; H, 6.79; N, 7.78; M.W., 356.16. Found: C, 40.79; 40.71; H, 6.79, 6.94; N, 7.98; M.W., 356 (mass spectrum).

IR: 2940 cm? (w.) (CH); 2820, 2760, 2070 5111- w. (NH,+ 1570 cm.- (s.)(NHf UV: no A522 210 In,

NMR (D 0): 7-=5.35 (s.) 4 exchange protons; 6.02 (m.) 4 tertiary CHN protons; 8.18 (m.) 16 CH protons EMMPLE 13 .1 3 14-DIBENZOYL- 1 3 ,14--DIAZA- TRICYCLO[6.4.1.1 ]TETRADECANE IR: 115?; 3070 em.- (w.) (C H 2920, 2860 cm.- (w.) (CH); 1635 cm. (vs.) (NCOC H 1595, 1490 1445, (w.) (C 11 NMR (CDCl,):

'r=2.65 (d., J=5 cps) aromatic protons; 5.04 (m.) 2 bridgehead protons; 6.36 (m.) 2 bridgehead protons; 8.33 (m.) 16 methylene protons EXAMPLE l4.--l 3 ,14-BIS(PHENYLCARBAMOYL)- 13,14 DIAZATRICYCLO[6.4.l.1 ]TETRADECA 3,5,9,l1-TETRAENE 0 II Formula II: R=C-N H0615 m=0 13,14 diazatricyclo[6.4.1.1 ]tetradeca-3,5,9,l1- tetraene (175 mg.; Examples 5 and 6) was dried at 100 C./ 0.2 mm. It was slurried with 2 ml. of carbon tetrachloride and treated with 0.30 ml. of phenyl isocyanate, warmed briefiy, and then cooled to 0 C. and filtered. The residue (219 mg, 55%) was purified by leaching it with ethanol in a Soxhlet extractor. The pure phenylurea derivative, 13,14-bis(phenylcarbamoyl)-13 ,14-diazatricyclo [6.4.1.1 ]tetradeca-3,5,9,1l-tetraene, was a white powder, M.P. 350 C. dec.

Analysis.Calcd. for C H N O C, 73.56; H, 5.70; N, 13.20; M.W., 424.28. Found: C, 72.82; H, 6.00; N, 12.97; M.W., 424 (mass spectrum).

IR: v55; 3220 cm.' (s.) (NH) 3130, 3060, 3030 cm.- (W.) (CH=CH); 1640, 1600, 1530 cm. (s.)(C H NHCO) EXAMPLE .--13,14 BIS (PHENYLTHIOCARBA MOYL) 13,14-DIAZATRICYCLO[6.4.1.I 'UTETRA- DECANE II Formula III: R""C-""NHC5H5, m=0

To a solution of 0.51 g. of 13,14-diazatricyclo [6.4.1.1 ]tetradecane (Example 11) in 2 ml. of ethanol was added 1.60 ml. of 50% ethanolic solution of phenyl isothiocyanate. The mixture was warmed for several minutes, then cooled to 0 C. and filtered. The white crystalline precipitate of the crude phenylthiourea derivative (1.02 g., 84%) was purified by prolonged extraction with ethanol in a Soxhlet apparatus to yield a white powder, 13,14 bis(phenylthiocarbamoyl) 12,14 diazatricyclo [6.4.1.1 ]tetradecane, M.P. 289289.5 C. dec.

Analysis.-Calcd. for C H N S C, 67.20; H, 6.94; N, 12.06; M.W., 464.68. Found: C, 67.35, 67.30; H, 7.04, 7.02; N, 11.83, 11.84; M.W., 464 (mass spectrum).

IR; 5; 3280 cm.- (m.) (NH); 3070 cm.- (W.) (061-15);

1305, 1505, 1450, (m-s.) ofinsNr-los UV: xCQHSOH 250 111,. ($33,000)

max.

EXAMPLE 16.l 3 14 BIS (PHENYLCARBAMOYL) 13,14-DIAZATRICYCLO- [6.4.1 .1 TETRADECANE 5;, 3320 cm." (s.) (NH); 3060 cm. (w.) (C 11 2930, 2860 cm? (W) (CH); 1640, 1595, 1530, 1505, 1440 cm. (UL-s.) (C H NHCO) UV: 102115011 243 mp (e=41,500)

max.

EXAMPLE 17. 13,14 DIMETHYL 13,14 DIAZA- TRICHLO[6.4.1.1 TETRADECA 3,5,9,11- TETRAENE Formula II: R=-CH3, m=0

13,14 diazatricyclo[6.4.1.1 ]tetradeca 3,5,9,11- tetraene (0.50 g.) and methyl iodide (5 ml.) were sealed in a tube and heated at 100 C. overnight. The contents of the tube were washed out with 20 m1. of methanol and evaporated to dryness to leave a brown crystalline residue (0.68 g.). This material was dissolved in water, the solution filtered, and the filtrate basified with 30% sodium hydroxide. The crude product weighed 0.171 g. (30% yield). Two recrystallizations from aqueous methanol followed by sublimation at 100 C./0.1 mm. gave pure crystalline 13,14-dimethyl-l3,14-diazatricyclo[6.4.1.1 tetradeca 3,5,9,11 tetraene, M.P. 166.5-168 C. dec. (sealed capillary).

Analysis.Calcd. for C H N C, 78.46; H, 8.47; N, 13.07; M.W., 214.30. Found: C, 78.60; H, 8.56; N, 13.09; M.W., 214 (mass spectrum).

IR: 1 35.5. 3060, 3015 em.- (w.-m.) (CH=CH); 3000, 2965, 2930, 2910, 2875, 2850, 2815, 2780 cm." (111.) (CH, NCH 1450 emf (s.) 1180, 1170 cm? (s.)

UV: 15 513 237 my. (6 =14,100) 230 m (6 13,900

NMR (hydrochloride in D20):

1 339 (d, J=4 c./s.) 3.57 (t, J=4 e./s.), 4 CH=CH protons 391 (m.) 4 CH-CH protons; 521 (s.) N-H exchange peak+2 bridgehead protons; 5.34 (s.) 2 bridgehead protons; 7.08 (s.) 6 NCH protons MS: m./e. 214 (parent), 107 (1/2 parent), 94, 92 (1/2 parentCH 81, 66, 65, 51, 43, 42, 39, 27, 15

Raman: strong band at 1615 cm.

Dipole Moment: 0.57D. On the basis of this measurement, the compound is indicated to have the trans stereoisomeric form (cf. Formula 11b).

EXAMPLE l8.l 3 l 4-DIMETHYL- 13 ,14-DIAZATRI- CYCLO [6.4. 1 .1 TETRADECANE Formula III: R=CH m=0 13,14-diazatricyclo[6.4.1.1 tetradecane (0.47 g.) was sealed in a tube with methyl iodide (5 ml.) and heated at 100 C. for one hour. The contents of the tube were rinsed out with methanol and water, and the extracts were evaporated to dryness to yield 0.96 g. of yellow-white solid. This product was dissolved in 20 ml. of water and treated with 30% sodium hydroxide. The white crystalline precipitate obtained weighed 0.30 g. and was purified by sublimation at C./0.1 mm. The colorless crystals of pure 13,14-dimethy1-13,14 diazatricyclo[6.4.l.1 ]tetradecane weighed 0.236 g. (44%), M.P. 96 C. (sealed capillary).

Analysis.-Calcd. for C H N C,75.61; H, 11.79; N, 12.60; M.W., 222.36. Found: C, 74.76; H, 11.82; N, 12.75; M.W., 222 (mass spectrum).

IR: 2920, 2860, 2780 emf (w.s.) (CH, NCH

1400 cm. (s.); 1180 cm.- (s.)

UV: no 15 5 between 200-400 m NMR c01 1-=7.37 (s.) 4 bridgehead protons; 7.44 (s.) 6 NCH protons; 8.41 (bm.) 16 CH protons MS: m./e. 222 (parent), 207 (parentCH 165, 112 ((16%garent4-H), 110, 96, 83, 70, 58, 42, 28, 15

13 14 EXAMPLE 19.-PREPARATION OF ACOPOLYMER tle and that from 190 being flexible. A film from 190 BETWEEN 13,14 DIAZATRICYCLO[6.4.1.l (0.0036" thick) showed the following properties. TETRADECA-3,5,9,11 TETRAENE AND ADIPIC Refractive Index: 1.57

ACID Resistivity: 10 ohm. cm.

302C (CH2). ('10 EN n i u- 2 4. N

g cocl N 5.. l

CO(CH2)4. C0211 n 13,l4-diazatricyclo[6.4.1.1 ]tetradeca-3,5,9,11 tetra- Tensile strength: ene (0.27 g.) was suspended in a mixture of dichloro- 5 7360 1b., 4.4% elongation at break methane ml.), water (40 m1.) and sodium hydroxide 5240 lb., 3.0% elongation at break (0.12 g.) in a 300-ml. tall-form beaker. This mixture was 7160 lb., 4.5% elongation at break agitated with a high-speed stirrer and treated at once Stiffness: with adipoyl chloride (0.25 g.). After 10 minutes stirring, 172,000 lb./in. the liquid was boiled for 5 minutes to remove dichloro 160,000 lb./in. methane, and then it was cooled to 0 C. and filtered to remove the white polymeric suspension. The residue was EXAMPLE 20-PREPARATION OF A COPOLYMER washed thoroughly with water and dried to a white powder BETWEEN 13,15-DIAZATRICYCLO[6.4.1.l ]TET- (0.46 g., 100%), M.P. 330 C. It was soluble in tetra- RADECAN-E AND ADIPIC ACID HO2C(CH2)4 CO m l. n .2l-Cl+n(Cl-L?) mNaOH- NH 000 1 N L.

CO(CH2)4 COQH fiuorodichloroacetone hydrate and in trifluoroacetie acid. 13,14 diazatricyclo[6.4.1.1 ]tetradecane hydrochlo- Analysis.- Calcd. for (C N N OQ C, 72.95; H, ride (0.53 g) was suspended in a mixture of dichloro- 6.80; N, 9.45. Found: C, 69.10, 69.25; H, 6.86, 6.94; methane 10 m1.) and water ml.), stirred rapidly, N, 8.59, 8.76. and treated in succession with sodium hydroxide (0.32 1 3500 (aw) (NH, 00211); 3030 g.) and adipoyl chloride (0.36). The white powdery (w) H= 720 -i (OO2H);1630 polymer was isolated as described in Example 19 (80 cm.- (v.s.) (NCOR); 750 cm.- (s.) (C=C) mg.), M.P. 315 C. dec. NMR (CF ClCOCFzC1-D2O)Z Analysis.Ca1cd. for (C H N O )n: C, 71.01; H,

-r=4.03 8 vinyl protons; 5.50 exchange signal HDO; l p

7.58 4 CH2 protons adjacent to 833 4 CH2 Found. C, 66.33, 66.34, H, 8.73, 8.79, N,

protons remote from C=O The method of Example 19 was employed to make addi- IR; 115?; 3450 cm, (m.) (NH, CO H) 2940, 2860 (w tional polymers from 1.0 g. of 13,14-diazatricyclo- (CH); 1740 cm.- (v.w.) (CO H); 1640 cm.- [6.4.1.1 tetradeca-3,5,9,ll-tetraene and 1.0 g. of vari- (v.s.) ous diacid ch1orides[A(COCl) Data for these preparations are given in the following table: The method of Example 19 was employed to make Polymer Inh.visc., AnaL, percent CFsCOzH, I.R.,cm.- NMR,T, 0. M0001); M.P.,C. 0 H N KBr,vmax. 01300211 25 0.

Example:

70.61 7.13 8.93 3,050 4.37 7.31 s 4.80 19a Adipoyl chloride 248 8:70

4.32 4.75 19b Suberoyl chloride 230 $3 8:93

4.28 72 54 4.74 190 Sebacoyl chloride 148-150 8:99

' 58.91 5.48 7.67 3,030 4.41 19d Ethylene glycol bis-chloroformate... -105 {58.87 5.36 7.62 1,710

Nona-The polymers of 19, 19a, 19b and are polyamides. That of 19d is a polyurethane.

The polymers of Examples 19b, 19c and 19d were additional polymers from 1.0 g. of 13,14-diazatricyclopressed into films at a pressure of 500 p.s.i. and tem- [6 .4.1.1 -"]tetradecane and 1.0 g. of various diacid chloperatures near their melting points. The films were selfrides [A('COC1) Data for these preparations are given supporting, those from 19b and 19d being somewhat brit- 75 in the following table.

Polymer Inh. visc Anal., percent CF3CO2H1 I.R., cm.- M 1, 0.25 A(COC1)2 M.P., C. O H N KBr, vmax. CFaCOzH 25 Example V 70. 21 9. 49 9. 14 2, 910 5. 34 8. 6. 02 a Adipoyl chloride 305 7. 45 8. 50 8. 77

70. 04 9. 08 8. 28 2, 910 5. 41 20b Suberoyl chloride 184-185 70.42 9. 01 8.28 1, 640 6. 02 1, 450 7. 59 8. 78

72. 31 9. 79 8. 64 2, 940 5. 40 20c Subacoyl chloride 69-71 72. 26 9. 79 8. 58 1, 640 6.05 1, 450 7. 60 8. 87

58. 1 7. 33 8. 24 2, 940 5. 54 20d Ethylene glycol bis-ohloroformate... 105-110 58. 06 7. 41 8. 21 1, 695 5. 76 1, 430 8.50

Norm-The polymers oi 20, 20a, 20b, and 200 are polyamides. That of 20d is a polyurethane.

The polymers of Examples 20a, 20b, 20c and 20d were pressed into films at a pressure of 500 p.s.i. and temperatures near their melting points. The films were all self-supporting though somewhat brittle. A film from 20b (0.0036" thick) showed the following properties:

Refractive Index: 1.548 Resistivity: 4x10 ohm. cm. Tensile strength:

5490 lb., 45% elongation at break 5510 lb., 41.3% elongation at break 4440 lb., 36% elongation at break Stiffness:

147,000 lb./in. 123,900 lb./in.

EXAMPLE 21.-PR'EPARATION OF 13,14 DIAZA- TRICYCLO[6.4.1.1 ]TETRADECA 3,5,9,ll-TET- RAENE DIHYDROCHLORIDE 13,14 diazatricyclo[6.4.1.1 tetradeca-3,5,9*,1l-tetraene (2.25 g.) was suspended in acetone (20 ml.) and treated with concentrated hydrochloride acid (3.2 ml.). The mixture was cooled to 0 C. and filtered. The residue was washed with acetone (100 ml.) and air-dried to a white powder (2.03 g., 65% It was purified by reprecipitation from 1% hydrochloric acid with acetone (1.43 g., 78% recovery), M.P. 300 C. dec.

Analysis.-Ca.lcd. for C H N Cl C, 55.60; H, 6.22; N, 10.81. Found: C, 55.92, 56.10, 55.88; H, 6.56, 6.10, 6.38; N, 11.19, 11.16.

IR: 1125;, 2850, 2680 cm.' (w.) (CH, NHf 1630 cm.

(w.) (CH=CH); 1550 cmr (s.) (NH UV: 1, 3 3% 235 mo $15,400), 230 m, (e=l6,600)

NMR (D 0): 1=3.59 complex multiplet 8 CH=CH proton; 5.10 HOD exchange protons+4 CHN protons EXAMPLE 22.-13,14-DINITROSO 13,14 DIAZA- TRICYCLO[6.4.1.1 ]-TETRADECA 3,5,9,11-TET- RAENE Formula II: R=NO, m=0

A mixture of 13,l4-diazatricyclo[6.4.l.1 ]tetradeca- 3,5,9,1l-tetraene (1.86 g.), water (10 ml.) and cone. hydrochloric acid (3.3 ml.) was stirred at 0 C. and treated gradually with a solution of sodium nitrite (1.52 g.) in water (5 ml.). After 1% hours stirring at 0 C. the mixture was filtered to yield the crude nitroso-compound as a brown powder (3.47 g.). Pure 13,14-dinitroso-l3,

14 diazatricyclo[6.4.1.l ]tetradeca 3,5,9,11 tetraene was obtained by two recrystallizations of 0.30 g. of this product from 80 ml. of ethanol. The product, 0.12 g. of

golden needles, M.P. 250 C. dec., was dried at C./

Analysis.-Calcd. for C H N O C, 59.01; H, 4.95; N, 22.94. Found: C, 59.07, 59.02; H, 5.03, 5.14; N, 22.56, 22.72.

UV: 155,59 375 m (shoulder) (5 172); 355 m (e= 142); 235 mu (e=19,000) NMR [(CD,) SO]; -r=4.18 (s.) 8 (CH=CH) protons;

4.30 (m.) 4 3 (CHN) protons EXAMPLE 23.13,14-DINITROSO-13,l4-DIAZA- TRICYCLO[6.4.1.1]TETRADECANE Formula III: R=NO, m=0

In a substantial repetition of the process of Example 22, a solution of 13,14 diazatricyclo[6.4.1.1 tetradecane (2.87 g.) in water (40 ml.) and concentrated hydrochloric acid (4.0 ml.) was treated with a solution of sodium nitrite (2.25 g.) in water (10 ml.) at 0 C. The crude yellow precipitate produced weighed 3.44 g. (92%). Two recrystallizations of 0.86 g. of this compound from a mixture of ethanol (8 ml.) and water (5 ml.) gave pure 13,14 dinitroso 13,14 diazatricyclo [6.4.1.1 ]tetr-adecane (0.66 g.), pale yellow crystals, M.P. 180-1825 C. dec.

Analysis.Calcd. for C H N O C, 57.11; H, 7.99; N, 22.21. Found: C, 57.32, 57.17; H, 7.79, 7.68; N, 22.24, 22.12.

IR: .3 2920, 2350, on 1450, 14.50, 14.30, 1370,

1355 N-No, CH)

UV: 13355 353 15,. (6 153); 355 (shoulder) @145 NMR 01301,

#139 (m.) 1 3 (CHN) protons; 3.50 (m.) 15 on protons EXAMPLE 24.13,l4-BIS(ETHOXYCARBONYL)-13, 14 DIAZATRICYCLO[6.4.1.1 ]TETRADECA 3, 5,9,11-TETRAENE Formula II: R g-00,115, m=0

A suspension of 13,14 diazatricyclo[6.4.1.1 ]tetradeca-3,5,9,l1-tetraene (7.44 g.) and anhydrous sodium carbonate (4.14 g.) in ether (70 ml.) was treated dropwise with a solution of ethyl chloroformate (8.50 g.) in ether ml.). After stirring for 6 hours, the mixture was allowed to stand overnight, evaporated to dryness, stirred with about 20 ml. of water and filtered. The pale yellow precipitate was recrystallized from ethanol ml.) to yield 7.72 g. (59%) of crystalline 13,14-bis (ethoxycarbonyl) 13,14 diazatricyclo[6.4.1.1 ]tetradeca-3,5,9,11-tetraene, M.P. 196.5197.5 C. after drying at 100 C./0.1mm.

Analysis.-Calcd. for C H N O C, 65.44; H, 6.71;

N, 8.48; M.W. 330.37. Found: C, 65.39, 65.66; H, 6.52, 6.54; N, 8.65; M.W. 330 (mass spectrum).

IR: v52; 3070, 3030 cm (CH=CH) 2980, 2960, 2940, 2930, 2915, 2870 cm.- (CH); 1700 cm.' (NCO C H 1650 cm. (C=C) UV: igg 237 my. $14,200 232 my =13,750

NMR (CD01 r=4.12 (be) 8 (CH=CH) protons; 5.14 (m.) 4 (CI-IN) protons; 5.90 (q., J=7) 4 (OCH protons; 8.82 (t., J=7) 6 CH protons MS: m./e. 330 (parent), 166, 165 ($6 parent), 152, 137, 130, 12s, 118, 117, 115, 108, 106, 105, 104, 103, 93, 92 (base peak), 80, 66, 65, 29, 28.

Diazatricyclotetradecatetraenedicarbonitriles of this invention (Formula IIa or Formula II with R=CN) can be made known from aromatic compounds through the sequence of conversion to N-cyanoazepine dimers by the method of the above-mentioned Marsh patent, i.e. by reaction of the aromatic compound with cyanogen azide, and rearrangement of such dimers as illustrated in the foregoing Examples 1 and 2. The N-cyanoazepine dimers are identified specifically as substituted lH-azepine-l-carbonitrile dimers having the Formula I, supra, and compounds of the invention obtained from such dimers are identified as substituted 13,14-diazatricyclo[6.4.1.1 tetradeca-3,5,9,1l-tetraene 13,14 dicarbonitriles having the Formula IIa, supra. The compound of Formula 1111 where X is fluorine and m'=1, for example, can be obtained by the following procedure: A solution of cyanogen azide in excess fiuorobenzene is heated at about 60 C. until an equivalent of nitrogen has evolved (ca. four hours). The product is a solution of monomeric fluorolH-azepine-l-carbonitrile and its dimer in excess fluorobenzene, from which the fiuorobenzene and the monomeric product are removed by molecular distillation at room temperature. The distillation residue is slowly added with stirring to approximately five times its volume of naphthalene preheated to 140 C., and the mixture is then heated further to a temperature of about 200 C. for half an hour. Dilution of the naphthalene mixture with excess benzene and filtration at about 60 C. yields the product (i.e., difluoro 13,14 diazatricyclo[6.4.1.1 ]tetradeca- 3,5,9,11-tetraene-13 ,14-dicarbonitrile) In Table A, which follows, are given aromatic compounds in the first column and X substituents in the second column to designate corresponding dimers of Formula I and product compounds of Formula IIa. It will be understood that Table A thus identifies specific representative compounds of the invention obtainable by the 18 TABLE A (Continued) Aromatic Compound X (Difiuoromethyl)benzene Difiuoromethyl (Trifluoromethyl)benzene Trifluoromethyl (Tn'chloromethyDbenzene Trichloromethyl Benzonitrile Cyano Nitrobenzene Nitro Methyl benzoate Methoxycarbonyl n-Hexyl benzoate n-Hexyloxycarbonyl o-Difiuorobenzene Fluoro p-Dichlorobenzene Ch1oro Ethyl p-fluorobenzoate m-Chloronitrobenzene 1,4-bis (trifluoromethyl) benzene Hexafiuorobenzene Additional representative diazatricyclotetradecatetraenes of this invention obtainable by methods described in Examples 3-9, 14, 17, 19, 22 and 24 are presented in Table B. In this table, precursors with variations in X corresponding to Formula II are shown in the first column. In the second column are shown corresponding products of Formula II with variations in the substituent R; and in the third column the methods of obtaining said products are identified by reference to appropriate examples.

As a specific example, the compound of Formula IIe (a diamine of Formula II, R=H) where X=fiuorine and m =6 can be obtained by prolonged (20 to 24 hours) hydrolysis of dodecafluoro-13,14-diazatricyclo[6.4.1.1 tetradeca-3,5,9,1l-tetraene-13,14-dicarbonitrile (Formula IIa, X=fiuorine, m=6) in 50% sulfuric acid at 100 C. Hydrolysis of this dicarbonitrile for a shorter time (4 to 10 hours) will yield dodecafiuoro-13,14-diazatricyclo [6.4.1.1 ]tetradeca-3,5,9,11 tetraene 13,14 dicarbonamide (Formula II,

R=(|.L/NH2 X=fiuorine, m=6). As a further specific example, the compound of Formula II, where R=phenylcarbamoyl, X=trifluoromethyl, and m=2, can be obtained from the corresponding diamine (Formula IIe, X=trifluoromethyl, m=2) by reaction with phenyl isocyanate. The foregoing compounds of the invention are, of course, derivable from corresponding intermediate lH-azepine-l-carbonitrile dimers which can be prepared initially from cyanogen azide and hexafluorobenzene or bis(trifiuoromethyl) benzene, respectively.

above-described sequence of aromatic compound to X -lH azepine-l-carbonitrile dimer to diX -13,14-diazatricyclo[6.4.1.l ]tetradeca 3,5,9,11 tetraene 13,14- dicarbonitrile.

TABLE A Aromatic Compound X n Fluorobenzene Fluoro Chlorobenzene ChlorO (2-chloroethyl)benzene 2-Chloroethyl Representative diazatricyclotetradecanes of the invention obtainable by methods illustrated in Examples 10-13, 15, 16, 18, 20 and 23 are shown in Table C. In this table, precursors of Formula III (R=H) with variations in Y, are shown in the first column. Corresponding products of Formula IV with variations in the substituent R are shown in the second column, and methods of obtaining said products are identified in the third column by reference to applicable examples.

As a specific example, the diazatricyclotetradecane of Formula III, where Y=trichloromethyl and m=1 (bis trichloromethyl 13,14 diazatricyclo[6.4.1.1 ]tetradecane) can be obtained from the initial starting materials benzotrichloride and cyanogen azide. The intermediate monomeric trichloromethyl-1H-azepine-l-carbonitrile obtained as a red oil dimerizes spontaneously on standing at room temperature. The resulting crystalline dimer can be converted to the compound of Formula 1111 (X=trichloromethyl, m=1) by heating a uniform mixture of it in a large volume of sodium chloride (table salt) at about 250 C. in a continuous-flow manner such that the mixture is subjected to heat for 10-20 minutes. The sodium chloride may be removed from the product by dissolu tion in water, followed by decantation r filtration. The bis trichloromethyl 13,14 diazatricyclo[6.4.1.1 tetradeca-3,5,9,11-tetraene-13 ,14-dicarbonitrile (Formula Ila, X=trichloromethyl, m.'=l) thus isolated can be hydrolyzed to the corresponding diamine (Formula IIe, X=trichloromethyl, m=1) in about 80% aqueous ptoluene-sulfonic acid under reflux. Hydrogenation of the diamine (cf. Examples and 11) yields bis-trichloromethyl-13,14-diazatricyc1o[6.4.1.1 ]tetradecane. This aliphatically saturated diamine can be further converted to additional compounds of Formula III, e.g., by treatment with ethyl iodide to form the compound where R=ethyl, Y=trichloromethyl, and m=1, i.e., bis-trichloromethyl- 13,14-diethyl-13, 14-diazatricyclo [6.4.1 .1 ]tetradecane.

and

Y N-R R-b'l Y wherein:

R is selected from the group consisting of cyano, hydrogen, nitroso, alkyl, carbamoyl, alkyland arylcarbamoyl, alkyland arylthiocarbamoyl, alkyl-, aryl-, alkoxyand All of the compounds of this invention melt with decomposition. The resultant gummy products are effective adhesives. For example, when the compounds of Examples 5 and 7 (Formula II: m=0; R- I-I and benzoyl, respectively) were placed between sheets of glass, decomposed thermally and cooled, the glass sheets were strongly cemented together.

Compounds of general Formula II all exhibit strong absorption (e=9000-32,000) in the 230-240 m region of the ultraviolet and can therefore be used in optical filter elements for removal of corresponding wavelengths of ultraviolet light. Absorption characteristics of certain of the compounds are shown in the following table:

Compounds of general Formula II where R=cyano (Examples 1 and 2) and carbamoyl (Examples 3 and 4) are intermediates to the diazatricyclotetradecatetraenes where R=H (the diamine of Example 5). The tetradecatetraene diamine reacts with a dicarboxylic acid chloride, e.g., adipoyl chloride, to form a polyamide (Example 19). The tetradecatetraene diamine can be hydrogenated to the corresponding saturated diamine (Formula III, R=H, Examples 10 and 11), which can also be reacted aryloxycarbonyl and aralkyl, all alkyl being of 1-8 carbons and all aryl being hydrocarbon of 6-10 carbons;

m is a number from 0 to 6, being a maximum of 2 when X is nitro;

X is selected from the group consisting of fluorine, chlorine, cyano, nitro, fluoroand chloroalkyl of up to 8 carbons and alkoxycarbonyl of up to 9 carbons; and

Y is selected from the group consisting of fluorine, chlorine, fluoroand chloroalkyl of up to 8 carbons and alkoxycarbonyl of up to 9 carbons;

valences of carbon in the depicted rings not satisfied by a double bond or a named substituent being satisfied by hydrogen.

2. The compound of Formula I of claim 1 wherein R is cyano and m is 0, 13,14-diazatricyclo[6.4.l.1 tetradeca-3 ,5,9,1l-tetraene-l3,14-dicarbonitrile.

3. The compound of Formula I of claim 1 wherein R is carbamoyl and m is 0, 13,14-bis(carbamoyl)-13,14- diazatricyclo[6.4.l.1 ]tetradeca-3,5,9,1l-tetraene.

4. The compound of Formula I of claim 1 wherein R is hydrogen and m is 0, 13,14-diazatricyclo[6.4.1.1 tetradeca-3 ,5 ,9,1 l-tetraene.

5. The compound of Formula I of claim 1 wherein R is benzoyl and m is 0, 13,14-dibenzoyl-13,l4-diazatricyclo] 6.4.1.1 tetradeca-3,5 ,9,1 l-tetraene.

6. The compound of Formula I of claim 1 wherein R is para-bromobenzoyl and m is 0, 13,14-di-para-bromobenzoyl-13,14 diazatricyclo[6.4.1.1 ]tetradeca 3,5,9,

1 l-tetraene.

7. The compound of Formula I of claim 1 wherein R is phenylthiocarbamoyl and m is O, 13,14-bis(phenylthiocarbamoyl) 13,14 diazatricyclo[6.4.l.1 ]tetradeca-3,5,9,1l-tetraene.

8. The compound of Formula II of claim 1 wherein R is hydrogen and m is 0, 13,14-diazatricyclo[6.4.1.1 tetradecane.

9. The compound of Formula II of claim 1 wherein R is benzoyl and m is 0, l3,14-dibenzoyl-13,14-diazatricyclo[6.4.l.1 "]tetradecane.

10. The compound of Formula I of claim 1 wherein R is phenylcarbamoyl and m is 0, 13,14-bis(phenylcarbamoyl) 13,14 diazatricyclo[6.4.1.1 ]tetracleca-3,5,9, l l-tetraene.

11. The compound of Formula II of claim 1 wherein R is phenylthiocarbamoyl and m is 0, 13,l4-bi s(phenylthiocarbamoyl) 13,14 diazatricyclo[6.4.1.1 ]tetradecane.

12. The compound of Formula II of claim -1 wherein R is phenylcarbamoyl and is 0, 13,14-bis(phenylcarbamoyl) -13,l4-diazatricyclo [6.4.1 1 tetradecane.

13. The compound of Formula I of claim 1 wherein R is methyl and m is 0, 13,l4-dimethyl-13,14-diazatricyclo 6.4. 1 1 tetradeca-3,5,9,1 l-tetraene.

14. The compound of Formula II of claim 1 wherein R is methyl and m is 0, 13,14-dimethyl-l3,14-diazatricyc1o[6.4.1.1 ]tetradecane.

15. The process of producing a 13,14-diazatricyclo [6.4.1.1 ]tetradeca-3,5,9,l1 tetraene 13,14 dicarbonitrile of Formula I of claini 1 wherein R is cyano which comprises heating, at a temperature in the range 175 C. to 300 C. and in admixtur with an inert diluent, a 11-1- azepine-l-dicarbonitrile dimer of the formula 22 where:

References Cited UNITED STATES PATENTS 6/ 1966 Kauer et a1. 260268 X 5/ 1967 Paquette 260268 X OTHER REFERENCES Johnson et a1. Jour. Am. Chem. Soc., vol. 88, pp. 2591-3 (1966).

DONALD G. DAUS, Primary Examiner US. Cl. X.R.

2 2 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2 l15 4 Dated October 28, i969 Invent0r(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

I Column 2, line 35 correct the spelling of --diazatr1cyclotetraenes- Column 5, line 56 correct the spelling of --tetradeca- Column 12, line 2 change "trichlo" to -tricyclo-- Column 16, in the table, the heading for the column next to the last on the right hand side, should read --NMR,

Column 17, line 17 transpose the two words "known from from known SIGNED AND SEALED MAY 26 1970 (SEAL) Attest:

t h Edw M F16 c m WILLIAM E. sum. I

Attesting Officer Comissioner of Patents 

